JP2001125264A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for an etching resist giving a cured film excellent in etching resistance, alkali solubility and pealable property, pattern forming property, etc., even in secondary etching at high temperature. SOLUTION: The curable composition contains (a) a compound having one carboxyl group and one (meth)acryloyl group in one molecule and (b) the di(meth)acrylate of a dihydric alcohol having hydroxyl groups at both ends of a 9-12C alkylene group as principal constituent components with the exception of the tri(meth)acrylate of an alkylene oxide adduct of isocyanuric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which can be cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam. The present invention relates to a curable composition suitable as an etching resist material in a secondary etching step in the production of a shadow mask because it can be easily separated from a substrate with an aqueous solution.

[0002]

2. Description of the Related Art A shadow mask has a function of causing electrons emitted from an electron gun in a cathode ray tube for a color television to collide with a light emitter of a predetermined color. (Aperture grill type) or a thin metal plate provided with a large number of fine holes such as circular holes in a predetermined pattern by etching. Among these shadow masks, shadow masks for CRTs of personal computers and the like include:
A shadow mask having a circular hole is used, and a shadow mask for a high-resolution or high-brightness television having a rectangular elongated hole (aperture grill type) is used.
These shadow masks are required to have finer and higher precision holes. In the manufacture of such a shadow mask, a concave portion is provided by primary etching at a corresponding position on the front and back surfaces of a metal plate, and a cured film of the backing material composition is formed on one surface thereof, and then a secondary film is formed. A method of performing etching to connect the bottoms of the corresponding concave portions to each other has been performed.

[0003] The outline of the manufacturing process of a shadow mask is as follows. First, a photosensitive resin is applied to both the front and back surfaces of a thin metal plate made of iron or the like, and then a negative film on which a pattern is arranged is brought into close contact with the metal plate to form a photosensitive resin. Is performed to harden the exposed portion, and the non-photosensitive portion of the photosensitive resin film is removed by a developing process. Next, primary etching is performed with a corrosive liquid such as iron perchloride to form fine concave portions that do not penetrate each other from both the front and back surfaces. The composition for the backing material is applied to only one side of the metal plate after the primary etching, and the composition is cured by irradiating active energy rays such as ultraviolet rays or heating, and the fine concave portions on one side of the metal plate are cured. A cured film to fill is formed. After protecting one side in this way, secondary etching is again performed on the concave portion on the other surface with the etchant, and the concave portion on the one surface and the concave portion on the other surface by the primary etching are communicated at the bottom. Then, each cured film of the photosensitive resin for pattern formation and the composition for the backing material is removed by alkali treatment to obtain a shadow mask. Here, by performing the secondary etching using the backing material composition, an abnormally large hole or a distorted hole that occurs when a hole is formed only by the primary etching is formed, and the accuracy of the hole is reduced. The problem of lowering can be solved. The backing material composition is usually referred to as an etching resist composition.

In the above method of manufacturing a shadow mask,
The curable composition used for the purpose of a backing material after the primary etching, that is, an etching resist material, must basically satisfy the following characteristics (Japanese Patent Publication No. 7-30270). Hole-filling property: The property of uniformly wetting the surface of a material having a hemispherical concave part having a diameter of 50 to 200 μm or an elongated rectangular concave part having a width of 50 to 200 μm and a length of 10 to 200 cm, and filling the concave part without generating bubbles in the concave part. Surface Smoothness: The property that the surface of the cured film is smooth, with no air bubbles resulting from micro gas generated when the backing material composition fills round holes or elongated rectangular recesses remaining in the cured resin surface layer. . In addition, it is also required that the cured film satisfies the requirements for a certain degree of flexibility, etching resistance, alkali peeling property and the like.

Recently, in the production of shadow masks,
The etching temperature has been increased for the purpose of shortening the etching time and for easily obtaining micro holes as designed. That is, about 40 to 55 ° C. has conventionally been mainly adopted as the etching temperature, but recently, 60 to 90 ° C. has been adopted. However, under such high temperature conditions, there has been a problem that a resist film formed from a conventional curable composition for an etching resist cannot maintain resist performance due to insufficient heat resistance. The present inventors have found that a curable composition that solves the above-mentioned problems of the conventional backing material composition, that is, the cured film has a high resistance to etching, alkali dissolution and peeling even in secondary etching at a high temperature. The present inventors have intensively studied to provide a curable composition having excellent pattern forming properties. As a result, the present inventors have found that a curable composition comprising the following compounds (a), (b) and (c) has the above properties, and filed a patent application earlier (Japanese Patent Application No. Hei 10 (1998) -108). -201215). (A) Compound having one carboxyl group and one (meth) acryloyl group in one molecule (b) Tri (meth) acrylate of alkylene oxide adduct of isocyanuric acid (c) Two or more (meth) acrylates Compound having acryloyl group

[0006]

The present inventors have further studied to solve the above-mentioned problems, and as a result, have found that the above-mentioned Japanese Patent Application No. Hei.
In the case where the compound (a) is used in combination with the specific compound belonging to the compound (c) in the invention according to 201215, a cured film having excellent etching resistance at a high temperature even when the compound (b) is not present is provided. The present inventors have found that a curable composition can be obtained, and have completed the present invention. That is, the present invention provides a curable composition for an etching resist containing the following compound (a) and compound (b) as main components [however, a composition containing tri (meth) acrylate of an alkylene oxide adduct of isocyanuric acid] Excluded). (A) Compound having one carboxyl group and one (meth) acryloyl group in one molecule (b) Di (meth) of dihydric alcohol having a hydroxyl group at both ends of an alkylene group having 9 to 12 carbon atoms In the present invention, an acryloyl group or a methacryloyl group is referred to as a (meth) acryloyl group, and an acrylate or methacrylate is referred to as a (meth) acrylate.
Acrylic acid or methacrylic acid is called (meth) acrylic acid. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (a) (hereinafter referred to as "component (a)") in the present invention is a compound having one carboxyl group and one (meth) acryloyl group in one molecule. Is a component that imparts dissolution / peelability by alkali treatment to a cured film obtained from the composition (1). Preferred components (a) include a reaction product (half ester compound) of a dibasic acid or an acid anhydride thereof and a (meth) acrylate having a hydroxyl group at a terminal, a compound having a lactone and a carboxyl group and a (meth) acryloyl group. And the like. Examples of the above-mentioned dibasic acids or acid anhydrides include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid and succinic acid, and acid anhydrides thereof, and have a terminal hydroxyl group (meth).
Examples of the acrylate include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

Specific compounds include (meth) acryloyloxyethyl monophthalate [commercially available products include:
Alonix M-5400 manufactured by Toagosei Co., Ltd. and the like. The same applies to parentheses below), (meth) acryloyloxypropyl monophthalate, (meth) acryloyloxyethyl monotetrahydrophthalate, (meth) acryloyloxypropyl monotetrahydrophthalate,
(Meth) acryloyloxyethyl monohexahydrophthalate, (meth) acryloyloxypropyl monohexahydrophthalate, (meth) acryloyloxyethyl monosuccinate [manufactured by Toagosei Co., Ltd., Aronix M-5500, etc.], (meth) acryloyl Oxypropyl monosuccinate, (meth) acryloyloxyethyl monomalate, (meth) acryloyloxypropyl monomalate and the like can be mentioned. As a specific example of a reaction product of lactone and a compound having a carboxyl group and a (meth) acryloyl group, a compound having a carboxyl group at a molecular terminal, which is a reaction product of ε-caprolactone and (meth) acrylic acid [Toagosei ( Co., Ltd., Aronix M-5300, etc.]. These can be used alone or in combination of two or more. In addition to the above compounds, (meth) acrylic acid or a dimer thereof (Toagosei Co., Ltd., Aronix M-5600, etc.) as the component (a)
Etc. can also be used.

More preferred components (a) are (meth) acryloyloxyethyl monophthalate and (meth) acryloyloxyethyl monohexahydrophthalate because they have a good balance between etching resistance and alkali solubility. The preferred mixing ratio of the component (a) is such that the total amount of the polymerizable components among the components constituting the curable composition is 10%.
0 parts by weight (hereinafter, “parts” means “parts by weight”) is 20 to 80 parts, more preferably 30 to 70 parts. If this ratio is less than 20 parts, the alkali dissolution and peeling properties of the cured film of the composition are not sufficient, and if it is more than 80 parts, the corrosion resistance during secondary etching may be insufficient.

The compound (b) (hereinafter referred to as "component (b)") is a di (meth) acrylate of a dihydric alcohol having a hydroxyl group at both terminals of an alkylene group having 9 to 12 carbon atoms. It is a component that imparts etching resistance to high-temperature etching to the film. Preferred component (b) is
Nonanediol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.
The preferred amount of the component (b) is 1 to 50 parts by weight per 100 parts by weight of the curable composition. When the proportion of the component (b) is less than 1 part by weight, the etching resistance of the cured coating film may be insufficient. On the other hand, when it exceeds 50 parts by weight, the alkali dissolution and peelability of the cured coating film are liable to decrease.

[0011] The curable composition of the present invention may be prepared by adjusting its viscosity or by etching resistance of a cured coating film, dissolving with alkali.
For the purpose of appropriately changing the releasability, a polymerizable component other than the components (a) and (b) may be blended. Examples of the polymerizable component that can be blended include the following compounds. The preferred amount is 0 to 40 parts by weight per 100 parts by weight of the curable composition. Monofunctional vinyl monomer Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, And alkyl (meth) acrylates such as stearyl (meth) acrylate, and hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Mono (meth) acrylates of polyalkylene glycol monoalkyl (having 1 to 18 carbon atoms) ethers such as polyethylene glycol and polypropylene glycol,
Polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; mono (meth) acrylate of ethylene oxide or propylene oxide adduct of phenol; ethylene oxide or propylene oxide of nonylphenol Mono (meth) acrylate of phenolalkylene oxide adduct such as mono (meth) acrylate of adduct and mono (meth) acrylate of ethylene oxide or propylene oxide adduct of p-cumylphenol, benzyl (meth) acrylate, ( (Meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, isobornyl (meth) acrylate And the like.

Polyol poly (meth) acrylate A reaction product of a polyhydric alcohol and (meth) acrylic acid. Specific compounds include butanediol di (meth) acrylate, pentanediol di (meth) acrylate, and hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate and di (meth) esterified diol of hydroxypivalic acid and neopentyl glycol Di (meth) acrylates of diols such as acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri or tetra (meth) acrylate, and tri or tetra (meth) acryle of pentaerythritol And poly (meth) acrylate of polyol such as penta or hexa (meth) acrylate of dipentaerythritol.

Polyester poly (meth) acrylate A reaction product of a polyester type polyhydric alcohol and (meth) acrylic acid can be mentioned. As the polyester type polyhydric alcohol, for example, polybasic acids such as succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid, and anhydrides thereof are used. it can. As the alcohol component, ethylene glycol, butanediol, hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, ethylene oxide of trimethylolpropane, or triol of a propylene oxide adduct, ethylene oxide of glycerin, Or propylene oxide adduct triol, and pentaerythritol ethylene oxide,
Alternatively, a polyester alcohol obtained by reacting a propylene oxide adduct tetraol or the like can be used.

Epoxy (meth) acrylate An addition reaction product of a polyvalent epoxy compound and (meth) acrylic acid can be used. Examples of the polyhydric epoxy compound include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of butanediol, diglycidyl ether of diethylene glycol, diglycidyl ether of triethylene glycol, diglycidyl ether of polyethylene glycol, and triglycidyl ether of triglycol. Diglycidyl ether of methylolpropane, diglycidyl ether of glycerin, diglycidyl ether of pentaerythritol, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of phenol novolak, diglycidyl ether of cresol novolak, etc. Can be

Urethane (meth) acrylate A reaction product of a polyhydric alcohol, a polyvalent isocyanate compound, and a hydroxyl group-containing (meth) acrylate can be used.
Examples of the polyhydric alcohol include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polyester diols such as ethylene glycol adipate, butanediol adipate, butanediol phthalate, and hexanediol phthalate. As polyvalent isocyanate compounds, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate,
Hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like can be used. Hydroxy group-containing (meth) acrylates include hydroxyethyl (meth)
Acrylates and hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate can be used.

The curable composition of the present invention preferably has a viscosity at 25 ° C. of 10,000 cps or less, more preferably 5,000 cps or less. 25
If the viscosity of the composition at 10 ° C. exceeds 10,000 cps, it may be difficult to uniformly wet the surface of the metal material having the concave portions and fill the holes. The viscosity of the composition can be easily adjusted by appropriately selecting the types and amounts of the various components described above, or by mixing the following other components.

The curable composition of the present invention comprises a chain transfer agent,
It is preferable to add a leveling agent and / or a polymerization initiator. ○ Chain transfer agent The composition of the present invention preferably contains a chain transfer agent for the purpose of imparting alkali dissolving / peeling properties and pattern forming properties to the cured film of the composition. As the chain transfer agent, various compounds conventionally known can be used, and a monothiol compound is preferable. Monothiol compounds include octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan, mercaptans such as cetyl mercaptan, hydroxyl-substituted mercaptans such as monothioethylene glycol and α-monothioglycerin, thioglycolic acid, mercaptopropionic acid And mercaptocarboxylic acids such as 2-mercaptopropionic acid, thiolactic acid and thiomalic acid. As the compounding ratio of the chain transfer agent, the total amount of the curable component is 100.
The amount is preferably 0.01 to 5 parts, more preferably 0.1 to 3 parts, per part. If the ratio is less than 0.01 part, the dissolution / peelability of the cured film becomes insufficient, so that the intervals between the holes formed in the metal plate become uneven or the metal portion between adjacent holes is twisted. May be. On the other hand, if it exceeds 5 parts, the stability of the composition may be reduced and the viscosity of the composition may be increased.

Leveling Agent The composition of the present invention preferably further contains a leveling agent for the purpose of improving the hole filling property of the composition and the surface smoothness of the cured film. As the leveling agent, a general surfactant can be used. Specific compounds include
For example, Florado FC-430 (manufactured by Sumitomo 3M), which is a nonionic fluorinated alkyl ester, Megafac F-177 [Dainippon Ink and Chemicals, Inc.
And Megafax F-179 (manufactured by Dainippon Ink and Chemicals, Inc.), and NU as a silicone compound
C silicone L7002 (manufactured by Nippon Unicar Co., Ltd.) and FZ-2165 (manufactured by Nippon Unicar Co., Ltd.). Among the above compounds, Megafac F-179 and N
What has little foaming property, such as UC silicone L7002, is preferable because a resin coating film having excellent surface smoothness can be easily obtained. As the compounding ratio of the leveling agent,
The amount is preferably 0.01 to 5 parts based on 100 parts of the total amount of the curable component. If the amount is less than 0.01 part, it may be difficult to impart the hole filling property and the surface smoothness characteristics to the composition of the present invention. If the amount exceeds 5 parts, the resin coating film may be liable to have defects. is there.

○ Polymerization initiator The composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays, visible rays or electron beams, or by heating, and the following components are mixed according to the curing means. Then, the composition can be cured in a short time. When the composition is cured by irradiating ultraviolet rays or visible light, the following photopolymerization initiators and sensitizers that are commonly used are used in order to sufficiently exhibit the photocurability of the composition. use. As a preferred photopolymerization initiator, specifically, as an acetophenone-based compound, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone (Irgacure 907 manufactured by Ciba Geigy), benzyldimethyl ketal (Irgacure 651 manufactured by Ciba Geigy), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Geigy), diethoxyacetophenone ( Fast Cure DEAP manufactured by First Chemical), 2-hydroxy-2-methyl-1
-Phenylpropan-1-one (Darocur 1173 from Ciba-Geigy), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959 from Ciba-Geigy) and 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone (Irgacure 36 manufactured by Ciba-Geigy)
9) and the like. As benzoin ethers,
Examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzophenones include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, 2,4,6-trimethylbenzophenone, and the like. The thioxanthones include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4
-Dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Other examples include camphorquinone. Among these photopolymerization initiators, acyl phosphine oxides are preferred in that when forming a shadow mask, the pattern formability can be improved, and the occurrence of a defect that an abnormally large hole is opened in a metal plate can be prevented. It is preferable to blend a system photopolymerization initiator and / or 1-hydroxycyclohexyl phenyl ketone. The sensitizer used in combination with the photopolymerization initiator includes triethanolamine, methyldiethanolamine, triisopropanolamine,
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone and 4,4
-Diethylaminobenzophenone and the like are preferred.

When the composition is to be cured mainly by a heat energy source such as a heating furnace, infrared rays and microwaves, it is preferable to add a thermal polymerization initiator. Examples include azo compounds such as butyronitrile, various organic peroxides such as ketone peroxide, hydroperoxide, alkyl peroxide, acyl peroxide and peroxyester, and inorganic peroxides such as ammonium persulfate. When left at room temperature or heated at a relatively low temperature of 100 ° C. or less, it is good to mix a polymerization accelerator together with the above-mentioned thermal polymerization initiator. As a preferable polymerization accelerator, for example, cobalt,
Organic metal salts of metals such as iron and manganese with naphthenic acid, linoleic acid, acetylacetone and the like, reducing amines such as dimethyl paratoluidine and ascorbic acid, and other reducing substances. These polymerization accelerators are used in combination, for example, in combination of a hydroperoxide, ketone peroxide or peroxyester and an organic metal salt, or an acyl peroxide and a reducing amine. The mixing ratio of the polymerization initiator is preferably 0.1 to 15 parts, more preferably 0.5 to 10 parts, based on 100 parts of the total amount of the polymerizable components. If the amount is less than 0.1 part, the effect of promoting the initiation of polymerization becomes insufficient, and
If it exceeds 5 parts, the components required for the cured film are reduced,
The target properties of the cured film may be reduced.

Other components In addition to the above components, water and an organic solvent can be appropriately blended to reduce the viscosity of the composition of the present invention. As the organic solvent, alcohols such as methanol, ethanol, butanol and isopropyl alcohol, butyl cellosolve, cellosolve such as methyl cellosolve and ethyl cellosolve, methyl cellosolve acetate, cellosolve acetate of ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol monomethyl ether, toluene, and Xylene and the like can be mentioned. The preferred proportion of the organic solvent is 100% of the total amount of the curable component.
0 to 10 parts per part. In addition, in order to reduce strain during curing, it is dissolved in a curable component and has a molecular weight of 10
A polymer of 100 to 100,000 and a particulate filler insoluble in the curable component can also be added. In order to obtain the composition of the present invention, the above components may be uniformly mixed by a usual mixing method, and there is no particular limitation on the order of mixing the components, the mixing apparatus, and the like. However, when mixing solid components at room temperature, the components can be mixed by heating to a temperature at which the components melt or disperse.

The curable composition of the present invention can be preferably used for forming a resist film at the time of secondary etching in the production of a shadow mask. Hereinafter, a method of manufacturing the shadow mask will be described. First, a photosensitive resin such as casein and polyvinyl alcohol is applied to the front and back surfaces of a thin metal plate made of iron or the like, and then a negative film on which a pattern is arranged is brought into close contact with the metal plate to cure the exposed portion of the photosensitive resin. Photolithography is performed, and a non-photosensitive portion of the photosensitive resin film is removed by a developing process. Next, primary etching is performed with a corrosive liquid such as iron perchloride to form fine concave portions that do not penetrate each other from both the front and back surfaces. A composition for a backing material is applied to one surface of the metal plate after the primary etching, and the composition is cured by irradiation with active energy rays such as ultraviolet rays or heating.
In this case, as a method of applying the composition, a normal application method such as spray, flow coat, bar coat, roll coat, die coat, and dip coat may be adopted. After the curing process of the backing material composition, a corrosive liquid is supplied to the metal plate, and secondary etching is performed on the concave portion on the other surface, and the concave portion on one surface and the concave portion on the other surface by the primary etching. At its bottom. The temperature in the secondary etching is 40 to 90 ° C., and the composition of the present invention is, as described above, in the high-temperature secondary etching,
Since it has both etching resistance and alkali dissolution / peelability, it can be preferably applied to secondary etching at a high temperature of 70 to 90 ° C. An alkali solution is supplied to the obtained metal plate having a large number of holes, and the cured film of the photosensitive resin film and the curable composition for a backing material is peeled from the metal plate. In this case, examples of the alkaline solution include aqueous solutions such as NaOH and KOH.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Examples 1 and 2 The components shown in Table 1 were mixed to obtain an active energy ray-curable composition. The obtained composition was applied on a test iron plate so as to have a film thickness of 30 μm, and the coating film was irradiated with ultraviolet rays using an 80 w / cm condensing metal halide lamp to obtain a cured coating film. . According to the method shown below the properties of the obtained cured film, hole filling,
The surface smoothness, etching resistance, alkali dissolution / peelability and pattern formability were evaluated. Table 2 shows the evaluation results of the physical properties and the viscosity of the composition before curing.

[0024]

[Table 1]

The abbreviations shown in Table 1 indicate the following compounds, respectively. -M-5400: Aronix M-5400, manufactured by Toagosei Co., Ltd., acryloyloxyethyl monophthalate-M-203: Aronix M-203, manufactured by Toagosei Co., Ltd., diacrylate of tricyclodecane dimethanol-M- 210: Aronix M-210, manufactured by Toagosei Co., Ltd., diacrylate of 4-mol ethylene oxide adduct of bisphenol A.-M-350: Aronix M-350, manufactured by Toagosei Co., Ltd., ethylene oxide 3 of trimethylolpropane. Triacrylate of molar adduct L7002: Nippon Unicar Co., Ltd., silicone-based polymer Luciline TPO: BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Irgacure 184: Ciba-Geigy, 1-hydroxycyclohexyl Shi Phenyl ketone The unit of numerical value representing the amount of compound in Table 1 are parts by weight.

[0026]

Comparative Examples 1 and 2 The components shown in Table 1 were mixed to obtain an active energy ray-curable composition. The obtained composition was subjected to the same physical property tests as those of the compositions of Examples, and the results are shown in Table 2.

[0027]

[Table 2]

<Hole-filling property> A test iron plate (200) having a negative pattern formed of a casein-based photosensitive resin film and having a number of elongated rectangular recesses formed by primary etching.
Hole filling when the composition of the present invention is applied to one side of an aperture grill type shadow mask iron plate (hereinafter simply referred to as a test iron plate), which is composed of a repeating pattern of concave portions and flat portions alternately provided at μ intervals. The state was visually determined. ：: There are no bubbles at all. Δ: Air bubbles are present in some holes. ×:
There are bubbles on the whole surface. <Surface Smoothness> The composition of the present invention was cured by irradiating ultraviolet rays to the iron plate after the hole filling property was evaluated, and the surface state of the cured film was visually determined. ：: No cissing. Δ: Repelling was partially observed. ×: Many repelling occurred. <Flexibility> The cured coating film was bent, and the crack of the coating film was observed. ：: The coating film is not removed. X: A coating film is formed.

<Etching Resistance> The iron plate after evaluating the surface smoothness was immersed in a 43% aqueous solution of FeCl ₃ at 90 ° C. for 20 minutes, and the surface condition of the cured film was visually determined. ：: No change at all. Δ: Colored. X: Swelling or peeling occurred. <Alkali dissolution / peelability> The iron plate after the evaluation of the etching resistance was immersed in a 20% aqueous NaOH solution at 80 ° C. for 1 minute, and the solubility or peelability of the cured film was visually determined. A: Completely dissolved and peeled. ：: Not completely dissolved but peeled. Δ: Some of the peeled ones remained on the metal plate. X: It did not peel. <Pattern-forming property> The iron plate after the alkali dissolution / peelability was evaluated was washed and dried, and light was applied from the back side of the iron plate, so that the shape of the elongated rectangular hole formed in the iron plate could be visually observed with transmitted light. In this way, the size of the holes, the distance between the holes, and the linearity of the long side of the rectangle were determined based on the uniformity of the brightness of the transmitted light. ◎: The size of the holes and the distance between the holes are completely constant, and the long sides of the rectangle are straight lines. ：: Approximately two out of 100 products have defects at about one place. Δ: About one defect was found in 3 to 9 out of 100 products. ×: 1-2 or more defects in 10 or more of 100 products.

[0030]

According to the present invention, the curable composition for a backing material at the time of manufacturing a shadow mask is easily and quickly cured by irradiating or heating with active energy rays. The film is excellent in all of etching resistance, alkali dissolving / peeling properties and pattern forming properties. Further, since the composition of the present invention does not require an organic solvent, a drying furnace for evaporating the organic solvent and a device for recovering the solvent are unnecessary, and there is no need to worry about the toxicity of the organic solvent when handling the raw material. Danger such as ignition and explosion during drying can be prevented. Moreover, it is possible to cure for a short time without the need for a drying step involving the evaporation of the organic solvent, to achieve a reduction in energy costs and prevention of fire, and to be useful in that it can be improved by utilizing existing processes. The industrial value is extremely large.

Claims (4)

[Claims] 1. A curable composition for an etching resist containing the following compound (a) and compound (b) as main components (excluding those containing tri (meth) acrylate of an alkylene oxide adduct of isocyanuric acid): ]. (A) Compound having one carboxyl group and one (meth) acryloyl group in one molecule (b) Di (meth) of dihydric alcohol having a hydroxyl group at both ends of an alkylene group having 9 to 12 carbon atoms ) Acrylate 2. The curable composition for an etching resist according to claim 1, wherein the compound (b) is nonanediol di (meth) acrylate or tricyclodecane dimethanol di (meth) acrylate. 3. The curable composition for an etching resist according to claim 1, further comprising an acylphosphine oxide-based photoinitiator or 1-hydroxycyclohexylphenyl ketone. 4. A method for producing a shadow mask, comprising using the curable composition according to claim 1, 2 or 3 as a backing material in a secondary etching step in producing the shadow mask.